Sparingly water-soluble azo dyestuffs



3,067,915 SPARKNGLY WATER-SGLUBLE A DYESTUFFS Ernest Marian, Bottmingen, Switzerland, assignor to andoz Ltd, Basel, Switzerland No Drawing. Filed May 26, 1958, Ser. No. 737,534

6 Claims. (Cl. 266-458) This invention relates to new azo dyestuffs which are sparingly soluble in water. They correspond to the general formula 1 E Z R;- o s-os ll N= N Il -M it it LL (I) wherein trifluoromethyl or trifiuoroacetyl amino radical, or an alkanoylamino radical with not more than l8 C atoms,

R for a divalent aliphatic radical with 1 to 4 carbon atoms,

R for a hydroxyalkyl radical, a dihydroxyalkyl radical, an alkoxyalkyl radical, an acetoxyalkyl radical which may be further substituted, a cyanoalkyl, the difluoromethyl or trifiuoromethyl radical, a fiuorinated .cyano alkyl, a carbalkoxyalkyl or a carbamic acid alkyl ester radical,

n for the number 1 or 2,

M for hydrogen, hydroxyl, an alkoxy radical, an acetoxy radical which may be further substituted, or a carbamic acid ester radical, when n represents the number 1, and for a single C N-linkage, when n represents the number 2, and

Z for hydrogen, methyl or methoxy, or together with -N-CH R and the vicinal benzene nucleus, for a tetrahydroquinoline ring.

Especially interesting dyestuffs are the monoazo dyestuffs which correspond to the formula wherein R has the above named meaning,

Y represents hydrogen, chlorine or methyl,

v represents hydrogen, methyl, ethyl, hydroxy, acetony or the radical of phenyl carbamic acid, and

w represents cyano, acetoxy or the radical of phenylcarbamic acid.

A number of these new, poorly water-soluble azo dyestuffs dye polyamide fibers (nylon, Perlon (registered trade namc)), cellulose esters such as cellulose acetate and triacetate, polyester fibers (Terylene, Dacron (registered trade names)) and polyvinyl fibers from aqueous suspension in brilliant red and violet shades. The dyeings are notable for their excellent fastness to light, washing, perspiration, cross dyeing, sea water, gas

3,fi7,9l5 Patented Now. it, 1961- fumes, sublimation and pleating. The dyeings are dischargeable white and the dyestuiis give a clear reserve of cotton and viscose rayon. The wool reserve is very good as well, especially in the case of blended tabrics when the dyed material is after-treated with sodium hydrosulfite to clear the wool fiber. On the Orlon polyester fibers only light depths of shade are obtainable; even so they show outstanding light fastness down to of standard depth. Some of the new dyestufls are also suitable for coloring lacquer media, oils, synthetic resins and artificial fibers in the mass. The cellulose ester filaments dyed in the mass are fast to light, washing, cross dyeing, alkaline chlorine bleaching, oxalic acid, peroxide bleaching, gas fumes and dry cleaning, and resistant to hydrosulfite.

The process for the production of the poorly watersoluble azo dyestults consists in diazotizing n mols of an amine of the formula S l RsO S-C5 2 n 2CNH2 N (II) wherein X and R possess the aforecited meanings, and coupling the diazo compound with 1 mol of a coupling component of the formula f E Z I I HzRzj Y H 11 (III) wherein R R M, X, Y and n possess the above-named meanings.

The diazo compounds are coupled with the coupling components in acid medium, if desired in presence of a buffer substance. The azo dyestulfs thus formed are isolated by one of the common basic operations, for example, filtration, reduction of the solvent to a small volume followed by filtration, distilling off the solvent and filtration, or precipitation from the solvent with a suitable agent and subsequent filtration.

In the following examples all parts and percentages are by weight and the temperatures in degrees centigrade. The melting points are uncorrected.

EXAMPLE 1 180 parts of concentrated sulfuric acid are heated and on reaching 6065 15.2 parts of sodium nitrite are added. The mixture is stirred for 1 hour at this temperature and the nitrosylsulfuric acid thus formed is then cooled to 5. At the same temperature 30 parts of propionic acid and parts of glacial acetic acid are added dropwise. The resultant solution is used to diazotize a solution of 35.6 parts of Z-amino-5-methylsulfonylthiazole in 30 parts of propio-nic acid and 170 parts of glacial acetic acid. After agitation for 4 hours at 0-5 the excess nitrosylsulfuric acid is destroyed with 20 parts of urea. The diazo solution thus obtained is mixed at O5 with a solution of 56 parts of l-bis-(acetoxyethyl)-amino-3-methylbenzene in 170 parts of glacial acetic acid. The coupling mixture is adjusted with sodium acetate to react neutral on Congo red indicator paper. The coupling reaction is completed in a short time. After 2 hours the reaction mass is diluted with 1000 pans of ice-water and the new dyestutt of the formula CHr-GHz-O-C O-CHs l CHr-CHz-O-CO-CH;

a) is separated in the normal manner. It is poorly soluble in ethanol and can be recrystallized from dioxane. The pure dyestutf melts at 164; when applied at high temperature from aqueous suspension, preferably in presence of compounds with dispersing action, it dyes polyester, acetate and triacetate fibers in brilliant Wine-red shades which show very good fastness to light, washing, perspiration, cross dyeing, sea water, gas fumes, sublimation and pleating. The dyeings are dischargeable white and the are suitable for dyeing polyester, acetate and triacetate fibers. They correspond to the formula 3 OHzCHO-COOHs Jl|C N=N CH2-C|)HOCOCH&

Table 1 Ex No. X Y u R Shade on acetate H C Red H OH- Scarlet H CH Red H- CH3 D H CH, D0 Ff C Do. CT-L CH0 D0. CH1 OFT, D0 GHQ Scarlet H- CH 0 CH CH1 Do Fr on. Do. CH, CH, D0. H O Wine-red. H CH1 Red-violet. H H CH D0. NH-OO CH H H CH Do NHOO-C2H LL H CH D0 NHC0-CF H H C Wine-red NHCO-CH H. CH4 Red-violet. NH-OO-OH 0-011 H OH, D0. H. FT H Cal? Red. H H H C Hn Do. H- H H Do. H. H H. De. H H H. Do. H H H D0. H H H D0. H Do. H Do. H Do. H. Do. H. Do. H Do. H D0. H NHCHZOHZOH. Do. H NHCH2CH(OH)OH3 Do. H H NHOHZOH OHZOCH Do. Pr H N(OH3)2 D0. H H H- N (CH )GH CH2OH Do. T-T Ff g N(C2H5)-OH2CH2OH D0. H H

dyestufi gives a clear reserve of cotton and viscose rayon. The wool reserve is very good as well, especially in the case of blended fabrics when the dyed material is aftertreated with sodium hydrosulfite to clear the wool fiber. On the Orlon polyester fibers only light depths of shade are obtainable; even so they show outstanding light fastness down to of standard depth.

The dyeing method for polyester fibers is as follows:

The dyebath is prepared with 1 part of the dyestuff of the present example dispersed with the aid of Turkey red oil, 6 parts of a sulfonated fatty alcohol and 3000 parts of water. A length of Dacron polyester fiber, 100 parts by weight, is introduced into this bath at room temperature. The temperature is increased to in 30 minutes and after the addition of 1.5 parts of Z-hydroxy- 1.ldiphenyl the bath is heated further to 100 and maintained at this temperature for 1 hour. The dyed material is then removed, rinsed with water and dried. It is dyed in a wine-red shade which is fast to light, W331 ing, perspiration, cross dyeing, sea water, gas fumes and heat setting treatments.

In Table I below further dyestuifs are disclosed which EXAMPLE 56 8.9 parts of 2-amino-5-methylsulfonylthiazole are dissolved in 200 parts of phosphoric acid and diazotized with 3.6 parts of solid sodium nitrite, added with stirring at 05. A creamy yellow mass is obtained which is mixed with a solution of 11 parts of l-bis-(hydroxyethyl)- amino-3-methylbenzene in 20 parts of glacial acetic acid. The dark red reaction mass is agitated for a further 30 minutes and then transferred into 1000 parts of water to form a dyestuff suspension which is subsequently filtered oil, washed free of acid and dried. The new dyestuif which has the formula is obtained in the pure form upon recrystallization from ethanol and then melts at 211. An analysis of the product yields the following values:

C found 47.03%; calculated 46.95%. H found 5.54%; calculated 5.21%.

3,007,915 6 0 found 16.70%; calculated 16.66%.

Table 3 S found 16.54%; calculated 16.66%.

Applied from aqueous suspenslon at lugh temperature, X Y 3 t W 33332 preferably 111 presence of compounds wlth dlspersmg actroh, the new dyestuff dyes acelate, tnacetate and poly m6" 01 H H E Red amlde fibers m wlne-red to red-v1olet shades wluch show 1Q'i 0-H 01 H H OH GET-OH a i 0 108 0-11 C1 H H OH CH3 D0. JEIY good fastness to washnzlg PBI'SPlIHLOD cross dyem 109 O1 CH3 H H OH D0 sea Water, gas fumes, subhmauon and pleatmg. The hght 0- 01 cm H OH GHQ-0H v n I 111.. 0-H Cl CH3 H OH CI-Ia Do. rastness I.) also good. 'lhe dyestuff reseryes Wool, cotton 10 n2" CmH CH3 H H H OH Redwiolet and VlSCOSB, and the dyemgs are dlschargeable glvmg clear 0- cm H H on GET-0H White is 81 a 5.1 s as s C a o. The dyestufis set out 111 Table 2 nave the formula 11 0 H 0H H 0H 011 011 013 Do 117.. 0-H OH; H OH 0H CH3 D0 s 1 3" El 8% E E EH 8% 0H s l J. 2 0. z- M 15 120.. N 01 H H 0H CH3 Do. z 121.. C-CH3 01 H H H Do. U C- u 12 01 H H OH CHFOH Do. X 01 H H 0H CH3 Do.

I CHTCH CH1 CH3 H H OH Red-violet 1 Y CH3 CH3 H OH CHr-OH Do. w CH3 CH3 H 0H CH: Do. T CH3 0113 H H 011 D0. and possess sumlar properues combmed 1n some cases oflcfifi CH8 CH3 H OH CHPQH Wlth lugher fastness Io hght.

Table 2 Ex. X Y Z u u w Shade on No. acetate H 0H3 H D0. OH2OH- H De. H H Violet. OCH H D0. H 011 -01-1- H Do. GHQ-OH-.. II D0. H Do.

Rod.

Do. Do. Wine-rod Do. Red.

D0. D0. D0. Do. Scarlet. Do.

Red.

D0. Scarlet. Red.

Do. Wine-red Do. Red. Wine-red ed. Wine-red ed. Wineqed ed. oooNHO H5. D0. OO0NHC H5 D0. OCONH-O2H5 Wine-red OCONHO2H5 Red.

OCONHC2H5 Do. H 0 00-NHC H5.-. Wine-red OOONH-C H OGO-NH-C;H5--- Red. O-OONHC H5 OCONHC H5 D0. o-00NH0 H5 O-CONHGZH5 Wine-red OOO-NHC H5 O-CONHO2H5 Red. H OH Wine-red 0 H. OH 0 Equally good afiinity and m certam cases stnl greater EXAMPLE 129 bnlllancy of shade are shown by the dyestulfs of formula when the 11 parts of 1 bls (hydroxyethyl) ammo 3 t methylbenzene used 1n Example 56 are replaced by 10 parts of N-cyanoethyl N hydroxyethylaminobenzene, a

a H30-02so dyestufi of formula ll X which are produced by the above-described procedures.

is obtained which on recrystallization from dioxane melts at 175. It dyes acetate and triacetate fibers from aqueous dispersion in brilliant red shades of outstanding fastness to light, gas fumes, sublimation and pleating. The dyestuif gives a very good reserve of cotton, viscose and wool and is readly dischargeable from other fibers. Its light fastness on polyamide fibers is slightly lower than on acetate.

and

GH -CH? OH In Table 4 below are enumerated dyestuffs with similar properties and in some instances better light fastness.

A dyebath is set with 1 part of the dyestuff of this eX- T y have formula ample, previously dispersed by means of Turkey red oil, 10 S CHPOHVCN 6 parts of a sulfonated fatty alcohol and 3000 parts of arms-0 Water. 100 parts of acetate fabric are entered at room g. C temperature and the temperature increased to 80 in l t GH:C{I\ hour, this temperature being maintained for a further w Table 4 Ex. No. X Y u w Ra Shade on acetate hour. After this time dyeing is completed; the material is removed, rinsed and dried.

To improve the dispersion, the dyestuif can be previously ground with suitable wetting, dispersing or emulsifying agents, preferably in presence of inorganic salts, for example Glaubers salt. Alternatively, it can be in- CHFGEK timately mixed with a dispersing agent to give an aqueous 45 w P which is E flf into a dyestuff Powder y possess in general lower aifini-ty for hydrophobic fibers. dfylng under Suitable condltlolls- They are however excellent for coloring oils, lacquer The Same Standard of Ollfld fastlless With a Slightmedia, synthetic resins and artificial fibers in the mass. 3 more YellOWlSh Shade 15 Obtained With the dyestllfis 0f Dyestuffs of such high molecular weight naturally possess the formulae 50 superior wet fastness properties to those hitherto known; in some cases the maximum fastness to boiling, cross dyeing and saponification is obtained. The dyestuifs described in the following Table 5 are specially interesting; they correspond to the above formula and are charac- 55 terized by the symbols X, Y, u, v, w and R Table --Continued Ex. X Y a 0 w R No. a

172-.- oH C1 t n o-oo-om .c 0 -0113 NEE- 3 173-. CH t. (31 H OCO-NHC5H5 O-CO-NH-(hHg.-- NH@ 174 0-11 o1 1r o oo om oo0-orn .t NHCH2C&H5 175 C-H C1 .i H OOOO2H5 OCOCzH5-.- i. -CH2- H2CeHs 176... 0-H o1 11 moo-om o-oo-orn NH@ 1 CHzOH 117 o11 o1 H o-oo-nnwemm o-o0-NH-o6n5..- NHGHQ 17s O-H o1 H O-OONHC H 0OONH-O@H5. NH H:-CHrCtH 179- 0-H o1 n O-OONHC@H5 0-CONHO H NH-Q 'OHROH 130--- C-CH3 o1 H OOONHO;H5. NHCBHB.-. N(0Hs):

181 c-@ o1 H OC0NHOH5 ooo-Nn-otm OHS 182"- 0-0 03, o1 n 0OO--NHG5H5.-. 0*00-NEP-CsHs..- M0115),

1ss.- o-Oom o1 H 0-o0-NH-otm 0-00-NH-dm--- H:

l CHa 184. o -o2m o1 H o-o0 o,m (Foo-01m 0113 185... 0001., 01 H o-co-Nn-ofim 0-o0NH-otrn- CH3 01 H 0-CO-NH-O0H5- OOONHC5H5. More),

NH-OO-O Eh... H o-oo-om o-o0-on3 N (orn o,m mr-oo-ogumm 0-o0-om on, NHCOCUH O-CO'CH3 CH3 Nrr oo-oflma-, H o-oo on3 on: NHOOC9Hm 04:04:33..- H om-0-oo o:a3 on,

A number of the dyestuffs of Examples 154 to 191 are readily soluble in acetone and are especially suitable for dope-dyeing acetate in brilliant fast-to-light red shades. Those dyestufis in which Y stands for chlorine yield slightly yellower shades and are the fastest to gas fumes.

100 parts of cellulose acetate are mixed with 300 parts of a mixture of solvents (93% acetone, 7% ethanol) for a short time and left overnight to swell. 1 part of the dyestuff obtained according to Example 157 is dissolved by simple shaking in parts of the solvent mixture and added to the cellulose acetate solution. The mixture is stirred in an open vessel until 60 parts of the solvent have evaporated.

The colored mass is pumped into the spinning machine in the normal Way and spun. The filament is dyed a bright red which is outstandingly fast to light, Washing, cross dyeing, alkaline chlorine bleaching, oxalic acid, peroxide bleaching, gas fumes and dry cleaning, and resistant to hydrosulfite.

Besides the already named dyestufis, the disazo dyestuffs produced by combining 2 mols of a Z-diazo-S-alkylor -alkylene-sulfonylthiazole, a 2-diazothiazo1e-5-su1fonic acid amide, a 2-diazo-5-alkylor -alkylenesulfonylthiodiazole or a 2-diazothiodiazole5'sulfonic acid amide with 1 mol of an amine of the formula These two dyestufifs dye acetate in the dope in brilliant phenylmethylamino group, the phenylethylamino group, red shades fast to light and outstandingly fast to wet the phenylamino group, the methylphenylamino group,

processes. the w-hydroxymethylphenylamino group, the N-methyl- Formulae of representative dyestufis of the foregoing phenylamino group, the N-ethyl phenylamino group and examples are as follows: the N-hyclroXyethyl-phenylamino group; Y is a member selected from the group consisting of a hydrogen atom,

EXAMPLE 2 a chlorine atom, a bromine atom, low molecular alkyl,

trifluoromethyl, trifluoroacetylamino and alkanoylamino s with not more than 18 carbon atoms; R is a member selected from the group consisting of ethylene, propylene 1| GN=N- -N and butylene; R is a member selected from the group consisting of lower hydroxyalkyl, lower dihydroxyalkyl,

N lower alkoxyalkyl, lower acetoxyalkyl, lower PIOPIOIIYI- Y oxyalkyl, lower cyanoalkyl, polyfiuoromethyl, fluorinated EXAMPLE 40 cyanoalkyl, lower carbalkoxyethyl and carbamic acid lower alkyl ester; 12 represents one of the integers 1 and 1130 s 2; M is a member selected from the group consisting of /GH2 CH2'O'G0CH3 hydrogen, hydroxy, lower alkoxy, acetoxy, propionyloxy H O HO CN=N N and carbamic acid ester, when n represents the number a 1, and stands for a single C-N-linkage, when n represents the number 2; and Z is a member selected from the group consisting of hydrogen, methoxy and, together with NCH R tetrahydroquinoline ring.

EXAMPLE 149 '2. The monoazo dyestufi of the formula S CHz-CHs-C-C O-CHa CHz-CHz-CN 6112-0 Hz-O-C O-CHa EXAMPLE 169 OHa-CHz-O-O 0-0H3 Having thus disclosed the invention what I claim is: 3. The monoazo dyestufl? of the formula 1. Sparingly water soluble azo dyestufi which corresponds to the formula oHl-om-o-oo-om 3'. 1 1 0H2 R2 in 4. The monoazo dyestuff of the formula wherein X is a member selected from the group consisting H30 5 of a nitrogen atom, C-H, C-lower alkyl, c cF,, c- 2 za phenyl, C-(methylphenyl), C-(ethylphenyl), C-(dimethylh ON=NN phenyl), C-(dichlorophenyl) and C-(chlorophenyl), R H30 110 is a member selected from the group consisting of alkyl with 1 to 4 carbon atoms, alkylene with 1 to 4 carbon atoms, fluorinated ethyl, chloroethyl, bromoethyl, hy- The mOIlOaZO dyestufi 0f the formula CHg-CHz-O-CO-CHa droxyalkyl with l to 4 carbon atoms, cyanoalkyl with s 1 to 4 carbon atoms, amino, lower alkylamino, lower CHz-CHz-O-C O-CH: hydroxyalkylamino, lower alkoxyalkylamino, di-lower B30028? alkylamino, N-lower alkyl-N-lower hydroxyalkylamino, C A

lower cyanoalkylamino, the cyclohexylamino group, the fl (Hiram-000mm 6. The monoazo dyestufi of the formula References Cited in the file of this patent UNITED STATES PATENTS (SEA-L) Attest:

ERNEST w. SWIDER DAVID LADD UNITED STATES PATENT OFFICE I CERTIFICATE or CoRRECTIoN Patent N00 3.007315 November Z 1961 Ernest Merian It is hereby certified that error appears in the above numbered pat-- ent requiring correction and that the said Letters Patent should read as corrected below.

In the heading to the printed specification between lines 5 and 6, insert the following Claims priority, applic ation Switzerland May 2.9 1957 Signed and sealed this 6th day of November 1962.,

Commissioner of Patents Attesting Officer 

1. SPARINGLY WATER-SOLUBLE AZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 